CN106332520B - A kind of graphite film composite and preparation method thereof - Google Patents
A kind of graphite film composite and preparation method thereof Download PDFInfo
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- CN106332520B CN106332520B CN201610598159.7A CN201610598159A CN106332520B CN 106332520 B CN106332520 B CN 106332520B CN 201610598159 A CN201610598159 A CN 201610598159A CN 106332520 B CN106332520 B CN 106332520B
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K7/00—Constructional details common to different types of electric apparatus
- H05K7/20—Modifications to facilitate cooling, ventilating, or heating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/04—Punching, slitting or perforating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/18—Handling of layers or the laminate
- B32B38/1808—Handling of layers or the laminate characterised by the laying up of the layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
- B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B2038/0052—Other operations not otherwise provided for
- B32B2038/0076—Curing, vulcanising, cross-linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/04—Punching, slitting or perforating
- B32B2038/047—Perforating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/302—Conductive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
Abstract
The present invention provides a kind of preparation method of graphite composite, penetrates between Multi-layer graphite film high polymer binder by dipping drilling technology, forms graphite film composite.This method is simple, reliable, strong operability, it can be applied to the preparation of the graphite film polymer composite of numerous systems, the graphite film composite prepared with this method has many advantages, such as that density is small, thickness is adjustable, thermal conductivity is high, mechanical property is preferable, inter-layer bonding force is stronger, can be widely applied in the heat management of electronic product.
Description
Technical field
The present invention relates to field of compound material more particularly to a kind of graphite film polymer composite and its manufacturing methods.
Background technique
With the fast development of electronic technology, electronic component volume constantly reduces, and chip integration is continuously increased, hot-fluid
Density is also increasing.High-power electronic component can generate a large amount of heat, if effective heat management measure is not taken, by heat
It passes, device will receive damage and even damage.Graphite is a kind of good Heat Conduction Material, has layer structure, respectively to different
Property, plane thermal conductivity is up to 50-1800W/ (mK).Moreover, the density of graphite is lower, theoretical density only has ~ 2.2g/cm3,
It is a kind of Heat Conduction Material with broad prospect of application.The graphite film or graphite flake developed in recent years, it is micro- that thickness can be as thin as tens
Rice, and there is preferably flexibility, compared with low-density, higher heat-conductivity is pasted on above chip or chipset, can be by chip heat
Amount is transmitted to surrounding, significantly reduces chip temperature, has been applied to the electronics such as smart phone, tablet computer, notebook, display
Product.
Common graphite film or graphite flake include following several major class: 1) first kind is expanded as made of expanded graphite roll-in
Graphite film, also known as expanded graphite paper, flexible graphite paper are to prepare expanded graphite by raw material of graphite, then by expanded graphite roller
Graphite film made of pressure (also known as calendering), such as patent of invention CN1926060 B(exfoliated graphite sheet) representated by expanded graphite
Film；2) the second class, graphite film, also referred to as pyrolytic graphite film as made of macromolecule membrane carbonization, graphitization and roll-in, refers to height
Molecular film is raw material, such as polyimides, polyamide, is carbonized, is graphitized graphite film, such as patent of invention made of simultaneously roll-in
CN102838107 the B(a kind of manufacturing method and system of high thermal conductivity graphite film) and patent of invention CN103193221 B(graphite film
And its manufacturing method) representated by graphite film；3) third class, graphite film made of being formed a film, restored as graphene oxide, also known as
RGO graphite film (rGO, reduced graphene oxide) claims graphene oxide to restore film, refers to natural scale stone
Ink is raw material, is prepared into graphene oxide, then graphene oxide forms a film, then through electronation or heat-treat
Graphite film, also referred to as graphene film, such as article Ultrathin Flexible Graphene Film:An Excellent
Thermal Conducting Material with Efficient EMI Shielding (Advanced Functional
Materials, 24 (2014), 4542-4548) and article Thermally reduced graphene oxide films
as flexible lateral heat spreaders (J. Mater. Chem. A, 2(2014), 16563-16568)
The graphite film reported；4) the 4th class, other conduction graphite films based on graphite, refers to other than above-mentioned three classes graphite film
Conduction graphite film based on graphite, such as a kind of carbon nanometer based on nano graphite sheet of patent of invention CN102874795 B(
Film and preparation method thereof) graphite film reported.The plane thermal conductivity of all these graphite films is more than 50W/ (mK), graphite
Film with a thickness of 1-2000 μm.
Graphite film is sheet, is presented obviously anisotropy, plane thermal conductivity 50-1800W/ (mK), perpendicular to
The thermal conductivity of in-plane is less than 10W/ (mK).The in-plane of graphite film refers to direction and graphite perpendicular to thickness
The highest direction of film thermal conductivity.
But graphite film has many deficiencies again, limits its extensive use.Firstly, the tensile strength of graphite film is not high,
Generally in 3-30MPa, though there is certain flexibility, it is easily broken, frangible；Secondly, the finite thickness of current various graphite films, generally several
Ten microns, expandable graphite sheet cause its heat flux smaller, limit its scope of application up to millimeter rank.Therefore, anxious
It needs a kind of with some strength, certain thickness, the lesser high thermal conductivity graphite composite block material of density, some heat dissipations hardly possiblies of solution
Topic.
In order to overcome the problems referred above, the method compound with metal, inorganic matter or high molecular material frequently with graphite film.Invention
Patent CN103258802A(patent document 1, graphite structure and using the graphite structure electronic device) method be
It is punched on Multi-layer graphite film, one layer of metal layer of regrowth, to prepare graphite film metal structure.Patent of invention CN103663407A
(carbon paper lamination compound heat-insulation liner) coats high polymer binder and high-temperature resistant coating on graphite film, cured, carbonization, at
Type, purification prepare carbon paper laminated composite.Patent of invention CN104691036 A(patent document 2, a kind of high thermal conductivity graphite is compound
Block and preparation method thereof) it high thermal conductivity graphite is made in the curved graphite film in one end under pressure answers by polymer bond layer
Block is closed, but the process is more complicated, needs for graphite film to be alternately stacked from level to level with binder, larger workload, and prepare
The inter-layer bonding force of graphite film composite block is not high.CN104669702 A(patent document 3 is applied for a patent, is accepted, a kind of graphite guide
Hotting mask composite block and preparation method thereof) graphite film is punched after with bonding film lamination, adhesive film can also lead in addition to connecting graphite film
Through hole exudation is crossed, is connected with heat source, plays the role of reducing the thermal contact resistance between graphite film and heat source, but the graphite prepared
Stomata inside the thermally conductive composite block of film is more, and thickness is too small, and only 5-100 μm, heat flux is too small when heat transfer, furthermore pure graphite
Film is very crisp, is not easy to punch.
Summary of the invention
When preparing graphite film polymer composite, the process is more complicated for existing method, and graphite film composite is anti-
Curved intensity is not high, layer by layer between be easily peeled off.
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of simple processes, reliable, and graphite film interlayer is not
Easily peelable, higher graphite film polymer composite of bending strength and preparation method thereof.
To achieve the above object, the invention discloses a kind of preparation methods of graphite film composite, including following step
It is rapid:
Stacking: S101 several graphite films is successively superimposed, graphite film laminated body is made；
S102, single-steeping: control condition makes high polymer binder become liquid, and it is made to be impregnated into the graphite film layer
In the lamellar spacing of stack；
S103, one-step solidification: to the graphite film laminated body by the single-steeping, control condition makes high polymer binder
Solidification, obtains graphite film composite.
Further, method of the invention can with the following steps are included:
Punching: S104 gets several dipping holes on the graphite film composite that the one-step solidification is formed；
S105, double-steeping: control condition makes high polymer binder become liquid, make it through dipping hole be impregnated into it is described
In the lamellar spacing of graphite film composite, and it is distributed in dipping hole；
S106, secondary curing: to the graphite film composite through double-steeping, control condition solidifies high polymer binder.
Further, graphite film used in the S101 step, plane thermal conductivity are more than 50W/ (mK), graphite film
With a thickness of 1-2000 μm；And/or
The graphite film include expandable graphite sheet, pyrolytic graphite film, graphene oxide reduction film and other with graphite be
One or more of conduction graphite film of main body；And/or
The volume fraction that the graphite film accounts for graphite film composite is 10-99%.
Further, binder used in S102 the and/or S105 step is high polymer binder.
Further, the composition of high polymer binder used in S102 the and/or S105 step is same or different, choosing
From epoxy resin, phenolic resin, alkyd resin, polyurethane, polysiloxanes, cyanate ester resin, acrylic resin, polyether-ketone, gather
Ether ether ketone, polyamide, polyamidoimide, polyimides, polyester, polycarbonate, polyolefin, polyphenylene oxide, polyphenylene sulfide, benzene second
Vinyl polymer, polysulfones, polyvinyl chloride, polyvinylidene chloride, chliorinated polyvinyl chloride, phenylpropyl alcohol cyclobutane, ethene-vinyl acetate are total
Polymers, polytetrafluoroethylene (PTFE), fluorinated ethylene-propylene resin, perfluoroalkoxy compound, polyethylene-tetrafluoroethene, polyvinylidene fluoride, poly- three
One of fluorine vinyl chloride, polyethylene-chlorotrifluoroethylene, polyvinyl fluoride, acrylonitrile-butadiene-styrene copolymer, polyformaldehyde
Or it is a variety of.
Further, if the high polymer binder is liquid at room temperature, curing agent or solidification are added thereto
Agent and diluent, are then impregnated；
If the high polymer binder is solid-state at room temperature, it is heated to and becomes liquid, then impregnated.
Further, the temperature of the heating is 50 DEG C -400 DEG C.
Further, dip time is 0.1-24h in S102 the and/or S105 step, and dipping temperature is 20-400 DEG C,
Apply pressure 0-100MPa.
The dipping hole that further the S104 step is formed is through-hole or blind hole, is by drill bit punching, laser boring
Or other hole knockouts obtain, the width in the dipping hole is 0.1-5mm, and the density in the dipping hole is 1-20/squares
Centimetre.
Further, in S103 the and/or S106 step, the curing time of binder is 1-72h, and solidification temperature is
20-180℃。
Further, in S103 the and/or S106 step, to graphite film laminated body or graphite while binder solidifies
Film composite applies the pressure vertical with graphite membrane plane, and the pressure is 0-100MPa.
The invention also discloses a kind of graphite film composites, and method is prepared by mentioned earlier.
The present invention prepares graphite film composite using dipping drilling technology, the difficult point for overcoming graphite film macromolecule compound, main
Advantage is wanted to have:
1) preparation method of the invention is simple, reliable, strong operability, and the graphite film macromolecule that can be applied to numerous systems is multiple
Fit preparation；
2) the graphite film composite prepared by impregnates in hole other than graphite film has high polymer binder between layer by layer
Filled with high polymer binder, the high polymer binder in hole is impregnated just like the effect of " rivet ", each layer graphite film is tightly connected
It is connected together, can more effectively enhance the intensity of graphite film composite, bending strength is higher, and inter-layer bonding force is more preferable, power
Learn function admirable；
3) hole is impregnated in this method to be formed after graphite film and high polymer binder one-step solidification, is effectively avoided
The difficult point directly punched on graphite film；
4) the resulting graphite film composite density of this method is small, thickness is adjustable, thermal conductivity can by the type of graphite film and
The percent by volume of graphite film controls.
In short, method of the invention is simple, reliable, strong operability, the graphite film macromolecule that can be applied to numerous systems is multiple
Fit preparation, and the graphite film composite of this method preparation is small with density, thickness is adjustable, thermal conductivity is high, mechanical property
It can be preferable, inter-layer bonding force is stronger the advantages that, can be widely applied in the heat management of electronic product.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is required attached drawing in technical description to be briefly described.
Figure 1A, 1B are the flow diagram of preparation method disclosed in this invention, and Figure 1A is the process of step S101-S103
Schematic diagram, Figure 1B are the flow diagram of step S101-S106.
Fig. 2A, 2B are the structural schematic diagram of the graphite film composite prepared by preparation method disclosed in this invention, figure
2A is the structural schematic diagram through graphite film composite prepared by step S101-S103, and Fig. 2 B is made through step S101-S106
The structural schematic diagram of standby graphite film composite.
Fig. 3 is the sectional schematic diagram of the graphite film composite prepared by preparation method disclosed in this invention, wherein 31
To impregnate through-hole, 32 be dipping blind hole.
Fig. 4 is the surface optical photo of graphite film epoxy resin composite disclosed in the embodiment of the present invention 1.
Fig. 5 is the section optical photograph of graphite film epoxy resin composite disclosed in the embodiment of the present invention 1.
Fig. 6 is that the section scanning electron microscope of graphite film epoxy resin composite disclosed in the embodiment of the present invention 1 is shone
Piece.
Specific embodiment
Technical solution of the present invention is further illustrated combined with specific embodiments below, but the present invention is not limited to be implemented as follows
The example content, the other embodiments based on inventive concept, also within the protection scope of the present invention.
Figure 1A is the flow diagram of step S101-S103, indicate successively by stacking, single-steeping step, it is primary admittedly
Change step and form graphite film composite, high polymer binder is located only within graphite film interlayer.Figure 1B is step S101-S103's
Flow diagram, indicate successively by stacking, single-steeping step, one-step solidification step, punch out step, double-steeping step and
Secondary curing step forms graphite film composite, and high polymer binder is not exclusively located in the lamellar spacing of graphite film, is also located at
It impregnates in hole.
In Fig. 2A, 2B, 21 be graphite film, and 22 be the high polymer binder of graphite film interlayer；In Fig. 2 B, 23 be dipping hole,
24 be the high polymer binder for impregnating hole.Fig. 2A is the structural representation through graphite film composite prepared by step S101-S103
Figure indicates that graphite film is combined by the high polymer binder in graphite film lamellar spacing.Fig. 2 B is through step S101-S106
The structural schematic diagram of prepared graphite film composite indicates that graphite film not only passes through the bonding of the macromolecule in graphite film lamellar spacing
Agent is also combined by the high polymer binder in dipping hole, and the bending strength of the graphite film composite block of formation is higher.
Fig. 3 indicates in claims that step S104 is formed by dipping hole and can be through-hole, is also possible to blind hole, may be used also
It is blind hole to be partially throughhole portions.
Embodiment 1
1. S101, size is 10cm × 10cm by stacking, with a thickness of 50 μm of 300 commercialization expandable graphite sheets (the
A kind of graphite film), it is successively superimposed, graphite film laminated body is made.
2. S102, single-steeping take 200g n-butanol and 600g dimethylbenzene, by the diluent of 1:3 proportional arrangement 800g,
Then 800g diluent is added in 800g bisphenol f type epoxy resin, and stirred evenly, add 200g polyamide work
It for curing agent, and stirs evenly, obtains the high polymer binder of liquid；Graphite film laminated body is placed in mold, mold is placed on
In vacuum impregnation furnace, vacuum impregnation furnace starts to vacuumize, until pressure is 10Pa, dipping in-furnace temperature is 25 DEG C, opens Vaccum Permeating
Liquid macroimolecule binder is flowed into mold by the Fluid valve of stain furnace, closes Fluid valve, impregnates 3h, pressure 10Pa,
Liquid macroimolecule binder is by the edge impregnation of graphite film into the lamellar spacing of graphite film.
3. S103, one-step solidification, the graphite film laminated body through single-steeping step is taken out, level is put into another mold
In solidified, apply the pressure vertical with graphite film in-plane when solidification to impregnated graphite film laminated body
(0.08MPa), in 80 DEG C of solidification 4h, high polymer binder becomes solid-state after solidification.
4. the graphite film composite formed by one-step solidification step is removed from the molds by S104, punching, thick with 2mm
Drill bit extend to lower surface along the direction perpendicular to graphite membrane plane from the upper surface of complex and bore circular dipping hole, leaching
The width in stain hole is 2mm, and the density for impregnating hole is 4/square centimeter, and dipping hole is blind hole.
5. S105, double-steeping take 200g n-butanol and 600g dimethylbenzene, by the diluent of 1:3 proportional arrangement 800g,
Then 800g diluent is added in 800g bisphenol f type epoxy resin, and stirred evenly, add 200g polyamide work
It for curing agent, and stirs evenly, obtains the high polymer binder of liquid；The graphite film obtained by a punch out step is compound
Body is again placed in mold, and mold is placed in vacuum impregnation furnace, and vacuum impregnation furnace starts to vacuumize, until pressure is 10Pa, dipping
In-furnace temperature is 25 DEG C, opens the Fluid valve of vacuum impregnation furnace, liquid adhesive is flowed into mold, closes fluid valve
Door impregnates 6h, and pressure 10Pa, liquid adhesive is impregnated into the lamellar spacing of graphite film by impregnating hole, and is distributed in dipping
Kong Zhong.
6. S106, secondary curing, the graphite film composite Jing Guo double-steeping step is taken out, level is put into another mould
In tool, apply the pressure (0.08MPa) vertical with graphite film in-plane to graphite film composite, 100oC solidifies 3h, allows viscous
Agent solidification is tied, final graphite film composite is formed.
The density of the graphite film composite obtained through step S101-S103 is 1.6g/cm3, plane thermal conductivity is 240W/
(mK), bending strength 6MPa.By step S101-S106, the density of the graphite film composite of formation is 1.5g/cm3, put down
Face thermal conductivity is 220W/ (mK), bending strength 20MPa.Above data is compared it is found that by punching, double-steeping and two
Secondary solidification can significantly improve the bending strength of graphite film composite.Fig. 4 is process step S101- disclosed in the present embodiment
S106 is formed by the surface optical photo of graphite film epoxy resin composite, impregnates hole as seen from the figure and is filled out by high polymer binder
It is full.Fig. 5 is the section light for being formed by graphite film epoxy resin composite disclosed in the present embodiment by step S101-S106
Photo is learned, the pattern for impregnating hole is high-visible, and dipping hole is filled up by high polymer binder.Fig. 6 is warp disclosed in the present embodiment
Cross the section scanning electron microscope photo that step S101-S106 is formed by graphite film epoxy resin composite.It is large stretch of in figure
Dark areas be graphite film, linear light tone region be epoxy resin layer.
Embodiment 2
1. size is 5cm × 5cm, with a thickness of 40 μm of 200 commercialization pyrolytic graphite films (second by S101, stacking
Class graphite film) successively superposition, graphite film laminated body is made.
2. S102, single-steeping take 200g n-butanol and 600g dimethylbenzene, by the diluent of 1:3 proportional arrangement 800g,
Then 800g diluent is added in 800g bisphenol f type epoxy resin, and stirred evenly, add 200g polyamide work
It for curing agent, and stirs evenly, obtains the high polymer binder of liquid, graphite film laminated body is placed in mold, mold is placed on
In vacuum impregnation furnace, vacuum impregnation furnace starts to vacuumize, until pressure is 10Pa, dipping in-furnace temperature is 25 DEG C, opens Vaccum Permeating
Liquid macroimolecule binder is flowed into mold by the Fluid valve of stain furnace, closes Fluid valve, impregnates 1.5h, and pressure is
10Pa, liquid macroimolecule binder is by the edge impregnation of graphite film into the lamellar spacing of graphite film.
3. S103, one-step solidification, the graphite film laminated body through single-steeping step is taken out, level is put into another mold
In, apply the pressure (0.1MPa) vertical with graphite film in-plane to impregnated graphite film laminated body, 120oC solidification
1h allows high polymer binder to solidify.
4. the graphite film composite formed by one-step solidification step is removed from the molds, uses 0.5mm by S104, punching
Thick drill bit extends to lower surface from the upper surface of complex and bores circular dipping hole along the direction perpendicular to graphite membrane plane,
The width for impregnating hole is 0.5mm, and the density for impregnating hole is 20/square centimeter, and dipping hole is blind hole, depth 7mm.
5. S105, double-steeping take 200g dehydrated alcohol as diluent, are added in 100g phenolic resin, and stir
Uniformly, 15g hexa is added as curing agent, and is stirred evenly, and liquid adhesive is obtained；It will be by primary punching
The graphite film composite that step obtains is again placed in mold, and mold is placed in vacuum impregnation furnace, and vacuum impregnation furnace starts to take out true
Sky, until pressure is 10Pa, dipping in-furnace temperature is 25 DEG C, opens the Fluid valve of vacuum impregnation furnace, liquid adhesive is flowed into
Into mold, Fluid valve is closed, impregnates 6h, pressure 10Pa, the layer that liquid adhesive is impregnated into graphite film by impregnating hole
In gap, and it is distributed in dipping hole.
8. S106, secondary curing, the graphite film composite Jing Guo double-steeping step is taken out, level is put into another mould
In tool, apply the pressure (0.1MPa) vertical with graphite film in-plane to graphite film composite, 60oC solidifies 12h, allows viscous
Agent solidification is tied, final graphite film composite is formed.
By step S101-S103, the density of the graphite film composite of formation is 1.7g/cm3, plane thermal conductivity is
650W/ (mK), bending strength 8MPa.By step S101-S106, the density of the graphite film composite of formation is 1.6g/
cm3, plane thermal conductivity is 625W/ (mK), and bending strength 30MPa, bending strength obviously increases.
Embodiment 3
Size is 5cm × 5cm, is successively superimposed with a thickness of 20 μm of 100 homemade graphite films by 1.S101, stacking, is made
At graphite film laminated body.Graphite film used be third class graphite film, prepared with graphene oxide, specific method referring to
Ultrathin Flexible Graphene Film: An Excellent Thermal Conducting Material
With Efficient EMI Shielding(Advanced Functional Materials, 24 (2014), 4542-
4548), the specific steps are as follows: 1) take the graphene oxide of 5g to be dissolved in 5000mL deionized water, 1h is stirred by ultrasonic；2) then will
It is poured in ptfe surface ware, and dry 10h, removes moisture removal, surface plate bottom just obtains graphene oxide at 50 DEG C
Film can obtain graphene oxide film stripping because graphene oxide membrane and the polytetrafluoroethylene (PTFE) binding force of bottom are very poor
To independent graphene oxide membrane；3) then, graphene oxide membrane is placed in graphitizing furnace, argon gas protection, with 5 DEG C/min's
Heating rate is warming up to 2000 DEG C, and keeps the temperature 1h.Later, stop heating, naturally cool to room temperature under argon gas protection, take out sample
Product after mechanical treatment, obtain the graphite film of 20 μ m-thicks.
2. S102, single-steeping take 500g acrylonitrile-butadiene-styrene copolymer (ABS) resin, done at 85 DEG C
Dry 3h removes moisture, is subsequently heated to 220oC, and 0.5h is kept the temperature, so that it is fused into liquid macroimolecule binder；By graphite film layer
Stack is placed in mold, and mold is heated to 180 DEG C, liquid macroimolecule binder is pressed into mold using press, pressure is
90MPa, liquid macroimolecule binder pass through the edge impregnation of graphite film into the lamellar spacing of graphite film, dwell time 8min.
3. S103, one-step solidification, the graphite film laminated body through single-steeping step is cooled to room temperature with mold, cold
But during, apply the pressure (8Mpa) vertical with graphite film in-plane, cooling time to impregnated graphite film laminated body
1h, high polymer binder solidifies after cooling.
4. the graphite film composite formed by one-step solidification step is removed from the molds, uses 1.0mm by S104, punching
Thick drill bit extends to lower surface from the upper surface of complex and bores circular dipping hole along the direction perpendicular to graphite membrane plane,
The width for impregnating hole is 1.0mm, and the density for impregnating hole is 10/square centimeter, and dipping hole is through-hole.
5. S105, double-steeping take 200g acrylonitrile-butadiene-styrene copolymer (ABS) resin, done at 85 DEG C
Dry 3h removes moisture, is subsequently heated to 220oC, and 0.5h is kept the temperature, so that it is fused into liquid macroimolecule binder；It will be by primary
The graphite film composite that punch out step obtains is again placed in mold, 180 DEG C of mold temperature, is glued liquid macroimolecule using press
Knot agent is pressed into mold, pressure 90MPa, the lamellar spacing that liquid macroimolecule binder is impregnated into graphite film by impregnating hole
In, dwell time 8min.
6. S106, secondary curing, the graphite film composite through double-steeping step is cooled to room temperature with mold, cold
But during, apply the pressure (8Mpa) vertical with graphite film in-plane to graphite film composite, cooling time, 0.5h, cooling
High polymer binder solidifies afterwards.
By step S101-S103, the density of the graphite film composite of formation is 1.8g/cm3, plane thermal conductivity is
840W/ (mK), bending strength are only 6MPa.By step S101-S106, the density of the graphite film composite of formation is
1.7g/cm3, plane thermal conductivity is 770W/ (mK), and bending strength 20MPa, bending strength obviously increases.
Embodiment 4
1. S101, size is 5cm × 5cm by stacking, with a thickness of 10 μm of 200 homemade nanometer sheet graphite films by
Layer superposition, is made graphite film laminated body.Homemade nanometer sheet graphite film used belongs to the 4th class graphite film, with nano graphite sheet
For raw material preparation, the specific method is as follows, and (referring to Chinese patent CN102874795 B, a kind of carbon based on nano graphite sheet is received
Rice film and preparation method thereof): 1) 20 DEG C, natural flake graphite is added in the mixed liquor I of the concentrated sulfuric acid and concentrated nitric acid, with
The stirring rate mechanical stirring 12hh of 300r/min, filtering, filtered solid is rinsed with deionized water to pH value is
6.5, then, 90 DEG C at a temperature of it is dry to constant weight, obtain dry graphite particle；Wherein, the mass percent of the concentrated sulfuric acid
Concentration is 95%, and the mass percent concentration of concentrated nitric acid is 65%, and the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 3.6:1, the concentrated sulfuric acid with
The ratio of the quality of the volume and natural flake graphite of the mixed liquor I of concentrated nitric acid is 10mL:1g；2) drying for obtaining step 1)
Graphite particle, be put into Muffle furnace, 1000 DEG C at a temperature of, constant temperature 50s is cooled to 20 DEG C, obtains expanded graphite；3)
The expanded graphite that step 3) is obtained is added in the mixed liquor II of the concentrated sulfuric acid and concentrated nitric acid, at 40 DEG C, with 300r/min's
Stirring rate mechanical stirring 1h, then, with the frequency ultrasound 3h of 40kHz, it is 2 that deionized water, which is added, and is diluted to the pH value of solution,
Obtain nano graphite sheet dispersion liquid；Wherein, the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 2.6:1, the concentrated sulfuric acid and concentrated nitric acid it is mixed
The ratio for closing the volume of liquid II and the quality of expanded graphite is 6mL:1mg；4) miillpore filter is laid in suction funnel, is being filtered
Under conditions of, the nano graphite sheet dispersion liquid for taking step 3) to obtain is added on miillpore filter, and is dispersed to nano graphite sheet
The upper surface of liquid applies the pressure of 0.7MPa, and pressure maintaining 5min obtains being laid in the graphite film on miillpore filter；5) by step
4) it is 7 that the graphite film being laid on miillpore filter obtained, which is rinsed with deionized water to pH value, then, will be flat after flushing
The graphite film of miillpore filter is layered at 70 DEG C, dry 20h sloughs miillpore filter, obtains dry graphite film, that is, complete
The preparation of nanometer sheet graphite film.
2. S102, single-steeping take 600g polycarbonate, dry 8h removes moisture at 110 DEG C, is subsequently heated to
300oC, and 0.5h is kept the temperature, so that it is fused into liquid macroimolecule binder, graphite film laminated body is placed in mold, mold heating
To 250 DEG C, liquid macroimolecule binder is pressed into mold using press, pressure 60MPa, liquid macroimolecule binder is logical
The edge impregnation of graphite film is crossed into the lamellar spacing of graphite film, dwell time 10min.
3. S103, one-step solidification, the graphite film laminated body through single-steeping step is cooled to room temperature with mold, cold
But during, apply the pressure (10Mpa) vertical with graphite film in-plane, cooling time to impregnated graphite film laminated body
1h, high polymer binder solidifies after cooling.
4. the graphite film composite formed by one-step solidification step is removed from the molds, uses 0.5mm by S104, punching
Thick drill bit extends to lower surface from the upper surface of complex and bores circular dipping hole along the direction perpendicular to graphite membrane plane,
The width for impregnating hole is 0.5mm, and the density for impregnating hole is 20/square centimeter, and dipping hole is through-hole.
5. S105, double-steeping take 300g ethylene-vinyl acetate copolymer (EVA), are heated to 200oC, and keep the temperature
0.5h makes it be fused into liquid macroimolecule binder；The graphite film composite obtained by a punch out step is again placed in mould
In tool, mold is heated to 150 DEG C, binder is injected into mold using injection molding machine, injection pressure 40MPa, and binder is logical
It crosses dipping hole to be impregnated into the lamellar spacing of graphite film, and is distributed in dipping hole, dwell time 3min.
6. S106, secondary curing, the graphite film composite through double-steeping step is cooled to room temperature with mold, cold
But during, apply the pressure (10Mpa) vertical with graphite film in-plane to graphite film composite, cooling time, 1h, cooling
High polymer binder solidifies afterwards.
By step S101-S103, the density of the graphite film composite of formation is 1.8g/cm3, plane thermal conductivity is
170W/ (mK), bending strength 15MPa.By step S101-S106, the density of the graphite film composite of formation is 1.7g/
cm3, plane thermal conductivity is 150W/ (mK), and bending strength 30MPa, bending strength obviously increases.
The above various embodiments explanation, graphite film composite prepared by the present invention is small with density, thickness is adjustable, thermal conductivity
High, the advantages that bending strength is higher, inter-layer bonding force is stronger.
Claims (13)
1. a kind of preparation method of graphite film composite, comprising the following steps:
Stacking: S101 several graphite films is successively superimposed, graphite film laminated body is made；
S102, single-steeping: control condition makes high polymer binder become liquid, and it is made to be impregnated into the graphite film laminated body
Lamellar spacing in；
S103, one-step solidification: to the graphite film laminated body by the single-steeping, control condition consolidates high polymer binder
Change, obtains graphite film composite；
Punching: S104 gets several dipping holes on the graphite film composite that the one-step solidification is formed；
S105, double-steeping: control condition makes high polymer binder become liquid, makes it through dipping hole and is impregnated into the graphite
In the lamellar spacing of film composite, and it is distributed in dipping hole；
S106, secondary curing: to the graphite film composite through double-steeping, control condition solidifies high polymer binder.
2. the method as described in claim 1, which is characterized in that
Graphite film used in the S101 step, plane thermal conductivity are more than 50W/ (mK), graphite film with a thickness of 1-2000 μ
m；And/or
The graphite film includes expandable graphite sheet, pyrolytic graphite film, graphene oxide reduction graphite film and other with graphite be
One or more of conduction graphite film of main body；And/or
The volume fraction that the graphite film accounts for graphite film composite is 10-99%.
3. the method as described in claim 1, which is characterized in that
High polymer binder used in the S102 step is selected from epoxy resin, phenolic resin, alkyd resin, polyurethane, gathers
Siloxanes, acrylic resin, polyether-ketone, polyether-ether-ketone, polyamide, polyamidoimide, polyimides, gathers cyanate ester resin
Rouge, polycarbonate, polyolefin, polyphenylene oxide, polyphenylene sulfide, styrenic polymer, polysulfones, polyvinyl chloride, polyvinylidene chloride,
Chliorinated polyvinyl chloride, phenylpropyl alcohol cyclobutane, ethylene-vinyl acetate copolymer, polytetrafluoroethylene (PTFE), fluorinated ethylene-propylene resin, perfluoroalkoxy
Compound, polyethylene-tetrafluoroethene, polyvinylidene fluoride, polytrifluorochloroethylene, polyethylene-chlorotrifluoroethylene, polyvinyl fluoride,
One of acrylonitrile-butadiene-styrene copolymer, polyformaldehyde are a variety of.
4. the method as described in claim 1, which is characterized in that
High polymer binder used in the S105 step is selected from epoxy resin, phenolic resin, alkyd resin, polyurethane, gathers
Siloxanes, acrylic resin, polyether-ketone, polyether-ether-ketone, polyamide, polyamidoimide, polyimides, gathers cyanate ester resin
Rouge, polycarbonate, polyolefin, polyphenylene oxide, polyphenylene sulfide, styrenic polymer, polysulfones, polyvinyl chloride, polyvinylidene chloride,
Chliorinated polyvinyl chloride, phenylpropyl alcohol cyclobutane, ethylene-vinyl acetate copolymer, polytetrafluoroethylene (PTFE), fluorinated ethylene-propylene resin, perfluoroalkoxy
Compound, polyethylene-tetrafluoroethene, polyvinylidene fluoride, polytrifluorochloroethylene, polyethylene-chlorotrifluoroethylene, polyvinyl fluoride,
One of acrylonitrile-butadiene-styrene copolymer, polyformaldehyde are a variety of.
5. the method as claimed in claim 3 or 4, which is characterized in that
If the high polymer binder is liquid at room temperature, curing agent or curing agent and diluent are added thereto, so
After impregnated；
If the high polymer binder is solid-state at room temperature, it is heated to and becomes liquid, then impregnated.
6. method as claimed in claim 5, it is characterised in that:
The temperature of the heating is 50 DEG C -400 DEG C.
7. the method as described in claim 1, which is characterized in that
Dip time is 0.1-24h in the S102 step, and dipping temperature is 20-400 DEG C, applies pressure 0-100MPa.
8. the method as described in claim 1, which is characterized in that
Dip time is 0.1-24h in the S105 step, and dipping temperature is 20-400 DEG C, applies pressure 0-100MPa.
9. the method as described in claim 1, which is characterized in that
The dipping hole that the S104 step is formed is through-hole or blind hole, is by drill bit punching, laser boring or other punchings
Mode obtains, and the width in the dipping hole is 0.1-5mm, and the density in the dipping hole is 1-20/square centimeter.
10. the method as described in claim 1, which is characterized in that
In the S103 step, the curing time of binder is 1-72h, and solidification temperature is 20-180 DEG C.
11. the method as described in claim 1, which is characterized in that
In the S106 step, the curing time of binder is 1-72h, and solidification temperature is 20-180 DEG C.
12. method as described in claim 10 or 11, which is characterized in that
Apply the pressure vertical with graphite membrane plane, institute to graphite film laminated body or graphite film composite while binder solidifies
Stating pressure is 0-100MPa.
13. a kind of graphite film composite, which is characterized in that
The graphite film composite is prepared by the method for any one of claim 1-12.
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| CN113394424B (en) * | 2021-06-11 | 2023-06-20 | 上海交通大学 | Adhesive conductive plate and method for producing the same |
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